Triarylmethane dyestuffs



Patented Oct. 22, 1940 PATENT OFFICE 2,219,009 TRIARYLMETCHANE DYESTUFFSWilhelm Eckert and Karl Schilling, Frankfortonthe-Main-Hochst, Germany,assignors to General Aniline & Film Corporation, a. corporation ofDelaware No Drawing. Application June 22, 1939, Serial No. 280,584. InGermany July 6, 1938 5 Claims.

The present invention relates to triarylmethane dyestuffs.

We have found that very clear and fast dyestuffs, capable of beingchromed, of the triarylmethane series are obtainable by condensing anN-acyl derivative of an amino-trimellitic acidor an anhydride or ananhydro-compound thereof with an aromatic hydroxyl compound containing areactive nuclear hydrogen atom and in meta-position to the hydroxylgroup a substituted amino-group or a second hydroxyl group. This issurprising since the free amino-trimellitic acids and the anhydridesthereof do not show this reaction even in the presence of condensingagents.

The acyl derivatives of amino-trimellitic acids used as parent materialswhich have, for instance, the following formulae Tooon COOH COOH and

and the anhydrides or anhydro-compounds thereof, for instance of thefollowing formula:

may be prepared by reaction of the corresponding halogen trimelliticacids With. ammonia, para-toluene sulfamide or a similar compound andsubsequent reaction of the products obtained with acid chlorides oranhydrides.

Aromatic hydroxyl .compounds containing a reactive nuclear hydrogen atomand, in metaposition to the hydroxyl group, a substituted amino-group ora hydroxyl-group, are, for instance, the following:meta-dimethyl-aminophenol, meta-dimethylamino-para-cresol and thecorresponding diethyl-, dipropyl-, dibutyl-, diisobutyl-derivatives;furthermore, the hydroxyl compounds of the above type containingdifferent substituents at the nitrogen, such as metaemethyl-ethyl-aminophenol, meta-methylethylamino-para-cresol or the like;further, metamono-methylaminophenol and meta-monomethylamino-para-cresoland the corresponding compounds containing alkyls of higher molecularWeight; further 3-hydroxy-diphenylamine and (of. U. S. Patent No.2,153,059, Example 10)), N- (3-hydroxyphenyl) -morpholine (obtainablefrom resorcinol and morpholine (of. U. S. Patent No. 2,153,059,));further, meta-disulfethylaminophenol,3-ethylsulfethylamino-4-methylphenol, meta methyl sulfethylaminophenol;meta-dihydroxyethyl'aminophenol; further, resorcinol,halogen-resorcinol, nitroresorcinol,

.resorcylic acid and the'like; pyrogallol, 1.3-dihydroxy-naphthalene andthe like.

For acids or the anhydrides thereof there may also be used condensingagents such as zinc chloride and the like.

The dyestuffs thus obtained dye animal fiber, in an acid bath, veryclear orange, yellow to bluish-red tints of good propertiesof fastness.The dyestuffs are also suitable for chrome-printing cotton, artificialsilk and the like and may be chromed in substance, the correspondingchr0- mium complex salts being then formed. These salts dye the fiber inan acid bath very clear tints which, without after-chroming, have verygood properties of fastness.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto the parts areby weight:

(1) 33 parts of diethylamino-meta-phenol and 25 parts ofanhydro-5-acetylaminotrimellitic anhydride are melted together for 4hours at C. The melt soon assumes a deep red.

colouration and acetic acid escapes. The cooled and solidified melt ispulverized, dissolved in 440 parts of sodium carbonate solution of 10per red solution at about 50 C. with a dilute mineral acid until acid todelta-papera dyestuff of the following probable constitution is obtainedCOO HOOC

condensing acylated amino-trimellitic which may perhaps also possess theisomeric constitution or is a mixture of the isomerides. The dyestuff isa bluish red powder which dissolves in alkalies to a red solution anddyes wool from an acid bath bluish red tints of remarkable fastnessproperties.

(2) 11.3 parts of B-aminotrimellitic acid and 50 parts of aceticanhydride are boiled together until dissolution occurs. 16.5 parts ofdiethylamino-meta-phenol are then added and the whole is boiled forseveral hours in a reflux apparatus, while stirring. After cooling, theacetic anhydride is cautiously decomposed with 500 parts of water, thered precipitate formed is filtered with suction and dissolved in dilutecaustic soda solution. After boiling the alkaline dyestuff solution forhour, the dyestuff is precipitated by rendering the solution acid todelta-paper by means of dilute mineral acid. The product obtained isidentical with the dyestuff of Example 1.

(3) 137 parts of ethylamino-meta-phenol and 115 parts ofanhydro--acetylaminotrimellitic anhydride are melted together for 3 to 4hours at 170 C. to 190 C. The melt becomes intensely red with evolutionof acetic acid. The melt is pulverized, dissolved in 2000 parts ofsodium carbonate solution of per cent. strength, filtered, if necessary,and after boiling the dyestuff solution for 10 minutes at about 50 0., adilute mineral acid is added until delta-paper assumes a yellowcoloration. The precipitated dyestufl. has the following probableformula HOOC or it may perhaps also possess the isomeric constitution orit may be a mixture of these isomerides. The dyestufi is a brown-yellowpowder which dissolves in alkalies to an orange-yellow solution and dyeswool from an acid bath the same tints of good properties of fastness.

(4) 151 parts of ethylamino-para-cresol and 115 parts ofanhydro-5-acetylamino-trimellitic anhydride are together melted for 4hours at 160 C. to 200 C., while stirring. The red dyestufi-melt ispulverized, dissolved in 2000 parts of sodium carbonate solution of 10per cent. strength, the solution is filtered and the filtrate is boiledfor a short time. By rendering the solution acid .to delta-paper bymeans of dilute mineral acid a dyestuff is precipitated which has theprobable constitution:

or may also possess the isomeric constitution:

or it may be a mixture of the isomerides. The dyestuif is a red powderwhich dissolves in alkalies to a red solution and dyes wool from an acidbath clear red tints.

(5) 23 parts of acylated 5-amino-trimellitic acid, 22 parts ofresorcinol and 13 parts of anhydrous zinc chloride are melted togetherfor 5 hours at 180 C. to 200 C. while stirring. Acetic acid is evolvedand an orange-yellow dyestufi is formed which is isolated by extractingthe pulverized melt with 200parts of boiling hydrochloric acid of 10 percent. strength, dissolving the residue in 200 parts of caustic sodasolution of 10 per or may also possess the isomeric constitution:

HzN

O OH

or it may be a mixture of the isomerides. The dyestufl' is a yellowpowder which dissolves in alkalies to a yellow-red solution and dyeswool from an acid bath purely yellow tints. We claim:

1. The compounds of the general formula wherein both Xs representidentical radicals of the group consisting of and 0-H, and both Y'srepresent identical members of the group consisting of hydrogen andmethyl. p 2. The compounds of the general formula wherein both X'srepresent identical radicals of the group consisting of and OH.

3.v The compound of the formula CzHs CzHs coo Hooo I being a bluish redpowder which dissolves in alkalies to a red solution and dyes wool froman acid bath bluish-red tints of remarkable fastness properties.

4. The compound of the formula being a brown-yellow powder whichdissolves in alkalies to an orange-yellow solution and dyes "wool froman acid bath the same tints of good fastness properties.

5. The compound of the formula v ECU OH o.

HOOC

NH: being a yellow powder which dissolves inalkalies to a yellow-redsolution and dyes Wool from an acid bath purely yellow tints.

WILI-IELM ECKERT. KARL SCI-IILLING.

